CN109761750B - Ester exchange catalyst with biological activity, synthetic method thereof and application thereof in preparation of degradable polyester - Google Patents
Ester exchange catalyst with biological activity, synthetic method thereof and application thereof in preparation of degradable polyester Download PDFInfo
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Abstract
The invention discloses a transesterification catalyst with biological activity, a synthesis method thereof and application thereof in preparing degradable polyester, wherein the synthesis method of the transesterification catalyst comprises the following steps: mixing the simple substance M with the dihydric alcohol A, heating to a temperature above the boiling point of the dihydric alcohol A, reacting under the condition of condensation and reflux, and stirring and aging to obtain the ester exchange catalyst; the simple substance M is at least one of metal magnesium, calcium and strontium; the structural general formula of the dihydric alcohol A is HO (CH)2)mOH, m is selected from 2-10; the mass ratio of the simple substance M to the dihydric alcohol A is 0.001-0.5: 1. the ester exchange catalyst is further applied to the field of synthesis of degradable polyester, and the finally prepared degradable polyester has high molecular weight and bioactivity and can be applied to the field of biomedicine.
Description
Technical Field
The invention relates to the technical field of ester exchange catalysts, in particular to an ester exchange catalyst with biological activity, a synthetic method thereof and application thereof in preparing degradable polyester.
Background
The degradable material is a product which can be degraded into small molecules harmless to the environment under the action of factors such as light, heat, oxygen, water, microorganisms and the like in the natural environment. At present, the research on the products is greatly carried out in all countries in the world. In the current research on degradable materials, polyester-based degradable materials play an important role. Aliphatic polyester polymers contain ester bonds in their molecular chains and are therefore easily hydrolyzed or degraded by microorganisms into small molecules such as water and carbon dioxide. For example, the surgical suture used in the biomaterial, the conventional surgical suture needs a secondary suture removal treatment after the wound is sutured, and is easy to generate inflammatory reaction and the like. Based on the concept of degradable materials, the degradable polylactic acid surgical suture is invented, and because polylactic acid can be digested by a human body, and the final products obtained by digestion are carbon dioxide and water which are harmless to the human body, secondary suture removing treatment is not needed, and the pain of the operation is reduced. The problem of white pollution can be easily solved if the degradable polyester material is used for replacing the traditional non-degradable material.
At present, the synthesis method of the degradable polyester material comprises condensation polymerization, ionic polymerization and coordination polymerization. Wherein, the condensation polymerization has the advantages of simple process and controllable conditions, thereby being the most common method for preparing the degradable polyester material at present.
The condensation polymerization for preparing polyester has more catalyst systems, and the catalysts with the best reported effect can be divided into three categories: titanium-based, antimony-based and germanium-based. When the titanium element is used as a catalyst, the catalytic activity is very high, but the titanium catalyst can accelerate the aging of polyester materials, and yellow the product, which affects the use, and a stabilizer is generally required to be added for stabilizing the polyester materials. Antimony is toxic, not beneficial to environmental protection, and can not be applied to biological materials. Germanium is expensive and not suitable for a wide range of applications. It has also been reported that organic solvents are used as catalysts, and because organic solvents are toxic and difficult to remove from the product, their use in biomedical applications is limited. Therefore, the search for a catalyst which is nontoxic, low in price and high in catalytic activity becomes a problem to be solved urgently.
Alkaline earth metals such as magnesium, calcium, strontium and the like are important constituent components of human bones and teeth, have remarkable osteogenic activity, can stimulate differentiation of stem cells into osteoblasts, promote growth and proliferation of the osteoblasts, help new bone formation and play an important role in the repair of the bones and the teeth. Biomedical materials based on alkaline earth metals, such as bioactive glass, bioceramic scaffolds, metal alloys, etc., have been developed and have been applied, in part, in clinical diagnosis and treatment in orthopedics and stomatology. If the synthesis of the degradable polyester can be catalyzed by calcium, magnesium and strontium metal, the obtained polyester material is not only nontoxic and can be used for human bodies, but also the metal ions contained in the product can promote the value increase of osteoblasts and have biological activity. Since the calcium magnesium strontium catalyst is not required to be removed, the application cost is reduced.
However, so far, no report exists only using calcium, magnesium, strontium metal or their compounds as catalyst, because calcium, magnesium, strontium metal or their compounds are directly used as catalyst activity too low to obtain high molecular weight polyester, and are generally used in combination with other catalysts.
For example, chinese patent publication No. CN 1951977 a discloses a method for producing polyester, wherein the catalyst used is composed of titanium compound, phosphorus-containing compound and magnesium compound, and the magnesium compound is selected from organic magnesium or inorganic magnesium. The composite catalyst uses a magnesium compound, but is also doped with titanium and phosphorus substances, because the titanium accelerates the aging of the material, and makes the material yellow, the use of the material is influenced, and the titanium metal can not be absorbed by organisms, the phosphorus substances are toxic, and simultaneously, a plurality of organic negative ion impurities are introduced, so the composite catalyst can not be applied to the catalysis of synthesizing the biological polyester.
Also, for example, chinese patent publication No. CN 105461911 a discloses an industrial polyester obtained by esterifying terephthalic acid and ethylene glycol, polycondensing, granulating, and washing with a mixture of magnesium glycol and antimony glycol. The composite catalyst is prepared by compounding magnesium glycol and ethylene glycol antimony, and the antimony metal is toxic, so the catalyst cannot be applied to the synthesis of biological polyester materials. And the synthesis of the catalyst is complicated, and the production cost of the polyester material is increased.
Disclosure of Invention
Aiming at the technical defects in the prior art, the invention provides the ester exchange catalyst which is synthesized by a special process and has bioactivity, is nontoxic and cheap, has bioactivity, does not introduce negative anion impurities, and does not need to be removed; the biodegradable polyester can be further applied to the field of synthesis of degradable polyester, and the finally prepared degradable polyester has high molecular weight and bioactivity and can be applied to the field of biomedicine.
The specific technical scheme is as follows:
a method of synthesizing a bioactive transesterification catalyst, comprising:
mixing the simple substance M with the dihydric alcohol A, heating to a temperature above the boiling point of the dihydric alcohol A, reacting under a condensing reflux condition, and stirring and aging to obtain the ester exchange catalyst;
the elementary substance M is at least one selected from metal magnesium, calcium and strontium;
the structural general formula of the dihydric alcohol A is HO (CH)2)mOH, m is selected from 2-10;
the mass ratio of the simple substance M to the dihydric alcohol A is 0.001-0.5: 1.
the invention discloses a transesterification catalyst synthesized according to the process, the general structure of the product is shown as the following formula (I):
M[OR(H)]t(Ⅰ)；
wherein t is selected from 1 or 2, R is selected from- (CH)2)mO-, and m is selected from 2 to 10.
The invention further discloses an application of the synthesized ester exchange catalyst, and a synthesis method of high molecular weight degradable polyester with bioactivity comprises the following steps:
prepolymerization reaction: carrying out pre-polymerization reaction on any one of dicarboxylic acid and dibasic ester and excessive diol B to prepare a prepolymer;
ester exchange reaction: and carrying out transesterification reaction on the prepolymer in the presence of a transesterification catalyst to obtain the biodegradable polyester with high molecular weight and bioactivity.
The synthesis of the degradable polyester adopts the conventional process means in the field, and the core invention is to adopt the ester exchange catalyst synthesized by the specific process. Experiments show that when the esterification catalyst synthesized by the specific process is used for preparing the degradable polyester, negative anion impurities are not introduced, and the catalyst is nontoxic and has bioactivity. The prepared polyester product has good mechanical property, the performance is comparable with that of the polyester material on the market, and the viscosity average molecular weight can reach 62KDa at most.
The reason for analyzing the above may be that the catalytic activity of the transesterification catalyst is closely related to the synthesis process thereof, the metal can be completely converted into metal alkoxide by the sufficient reaction at the condensation reflux temperature, and a single-active-center crystal form having a catalytic property can be obtained by the sufficient stirring and aging without damaging the crystal form to generate defects, and the dispersibility of the catalyst can be improved, thereby improving the activity of the catalyst to a large extent. Further comparison experiments show that if the simple substance M is directly added into a polycondensation reaction system, the catalytic activity is low due to incomplete metal conversion, and the viscosity-average molecular weight of a polyester product finally prepared by using the simple substance M as an esterification catalyst is low.
If the magnesium dialkoxide prepared by the electrolysis method in the patent document with the patent publication number of CN 105461911A is used as the catalyst, because the catalyst has low dispersibility and a plurality of side reactions can occur during electrolysis, a plurality of active centers exist in the system, the catalyst has a plurality of crystal forms and a plurality of defects, so that the catalyst has low activity, and the viscosity-average molecular weight of a polyester product finally prepared by taking the catalyst as the esterification catalyst is also lower, which is the fundamental reason why other high-activity catalysts need to be added for composite use in the technical scheme.
In the invention, the catalytic activity of the ester exchange catalyst is closely related to the synthesis process, metal can be completely converted into metal alkoxide through sufficient reaction at the condensation reflux temperature, a single-activity center crystal form with catalytic property can be obtained through sufficient stirring and aging, the defect of the crystal form can not be damaged, and the dispersity of the catalyst can be improved, so that the activity of the catalyst can be improved to a great extent. The transesterification catalyst is used in the polyester production process and the activity of the transesterification catalyst will be a critical step in determining the molecular weight of the polyester.
Through experimental comparison, compared with the method that the simple substance M is directly added into a polycondensation reaction system or the magnesium dialkoxide prepared by adopting an electrolysis mode in patent document with patent publication No. CN 105461911A is used as a catalyst, the catalyst has low dispersity and generates a plurality of side reactions during electrolysis, a plurality of active centers exist in the system, the catalyst has a plurality of crystal forms and a plurality of defects, so that the activity of the catalyst is low, the molecular weight of the finally prepared polyester product is low, and the method is also the fundamental reason that other high-activity catalysts need to be added for composite use in the technical scheme. In the pre-polymerization reaction:
the structural general formula of the dicarboxylic acid is HOOC (CH)2)xCOOH, x is selected from 0 or 2-8; specifically, the acid is at least one selected from oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
The dibasic esterHas a structural general formula of CH3(CH2)yOOC(CH2)zCOO(CH2)yCH3Y is selected from 0 or 1, and z is selected from 0-8; specifically, the organic solvent is at least one selected from dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, diethyl oxalate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, diethyl pimelate, diethyl suberate, diethyl azelate and diethyl sebacate.
The structural general formula of the dihydric alcohol B is HO (CH)2)nOH and n are selected from 2-10; specifically, the solvent is at least one selected from propylene glycol, butylene glycol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.
By "excess" is meant a molar excess, i.e., a molar ratio of dicarboxylic acid or diester to diol B of less than 1. The ester exchange reaction can be continuously carried out by the excessive amount of the dihydric alcohol B, so as to obtain the polyester with high molecular weight, and the molar ratio of any one of the dicarboxylic acid and the dibasic ester to the dihydric alcohol B is preferably 1: 1.1 to 5.
Because of the loss of the dihydric alcohol B in the prepolymerization reaction, the dihydric alcohol B can be selectively supplemented in the ester exchange reaction, the excessive alcohol in the reaction system is ensured, the ester exchange reaction is ensured to be carried out all the time, and 0.5-10% of the mass of the dihydric alcohol B is generally supplemented on the basis of the mass of the dihydric alcohol B added in the prepolymerization reaction.
Preferably, the temperature of the prepolymerization reaction is 80-230 ℃; and the prepolymerization reaction is carried out under the protection of inert atmosphere until no micromolecule by-product is generated, and the next step of ester exchange reaction is carried out.
If dicarboxylic acid and dihydric alcohol are used as raw materials to carry out prepolymerization reaction, the produced micromolecule by-product is water.
If the dibasic ester and the dihydric alcohol are taken as raw materials to carry out prepolymerization reaction, and dimethyl oxalate is further taken as an example, the generated micromolecule by-product is the methanol.
In the transesterification reaction:
the transesterification catalyst may be specifically at least one selected from the group consisting of magnesium propylene glycol, magnesium butylene glycol, magnesium pentylene glycol, magnesium hexylene glycol, magnesium heptylene glycol, magnesium octylene glycol, magnesium nonylene glycol, magnesium decylene glycol, calcium ethylene glycol, calcium propylene glycol, calcium butylene glycol, calcium pentylene glycol, calcium hexylene glycol, calcium heptylene glycol, calcium octylene glycol, calcium nonylene glycol, calcium decylene glycol, strontium ethylene glycol, strontium propylene glycol, strontium butylene glycol, strontium pentylene glycol, strontium hexylene glycol, strontium heptylene glycol, strontium octylene glycol, strontium nonylene glycol and strontium decylene glycol.
Preferably, the diol A is the diol B. Namely, the dihydric alcohol A used for preparing the transesterification catalyst and the dihydric alcohol B used for preparing the polyester are selected from the same variety. So as to ensure that no redundant anions are introduced and no further impurity removal is needed.
Further preferably:
when the raw material is selected from dicarboxylic acid and dihydric alcohol, the esterification catalyst is preferably selected from calcium dihydric alcohol. Tests show that the polyester product prepared by using the dihydric alcohol compound containing calcium as the catalyst has higher viscosity-average molecular weight.
When the raw material is selected from dibasic ester and dihydric alcohol, the esterification catalyst is preferably selected from dihydric alcohol magnesium. Tests show that the polyester product prepared by using the glycol compound containing magnesium as the catalyst has higher viscosity-average molecular weight.
Preferably, the transesterification catalyst is used in an amount of 0.001 to 5 wt% based on the total mass of the raw materials. The "total mass of raw materials" herein is the total mass of the dicarboxylic acid and the diol a, or the total mass of the diester and the diol a.
Preferably, the transesterification reaction is carried out under reduced pressure, and the vacuum degree is 0.1-80 Pa.
The temperature of the ester exchange reaction is 120-260 ℃, and the time is 6-24 hours.
The invention also discloses the biodegradable polyester with bioactivity synthesized by the method, wherein the polyester has high molecular weight, and the viscosity average molecular weight can reach 62 KDa; and has bioactivity and degradability.
Compared with the prior art, the invention has the following outstanding advantages:
(1) the invention discloses a synthesis method of an ester exchange catalyst, wherein the prepared ester exchange catalyst is at least one of dihydric alcohol magnesium, dihydric alcohol calcium and dihydric alcohol strontium, and has excellent catalytic activity; calcium, magnesium and strontium are all important metal elements in a living body, have the characteristics of no toxicity and absorbability, have biological activity, have the promotion effect on the proliferation of bone osteoblasts of a human body, do not need to remove catalysts, have low cost and can be used in large quantities.
(2) The invention firstly and independently uses at least one of dihydric alcohol magnesium, dihydric alcohol calcium and dihydric alcohol strontium as an ester exchange catalyst for preparing polyester products; the preparation process is simple, the degradable polyester can be directly obtained, the production efficiency is high, the cost is low, the dihydric alcohol generated in the production process can be recovered, the utilization rate of raw materials is high, and the green chemistry principle is met; the prepared polyester product has the characteristics of high molecular weight, degradability, no biotoxicity, strong safety and the like, has good market space and value, and can be applied to the field of biomedicine.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. Its purpose is merely to better understand the invention and not to limit its scope.
Example 1
(1) A250 mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet tube, a condenser and the like was charged with 10 g of analytically pure 1, 4-butanediol, 0.35 g of magnesium powder was added, argon gas was introduced, the mixture was heated to 120 ℃ and reacted for 6 hours under stirring at 100 r.p.m., and 2.5 g of magnesium butoxide having catalytic activity was obtained after cooling, stirring and aging for 1 hour.
(2) Another 250mL three-neck flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet tube, a condenser and the like is taken, 16.3 g of dimethyl succinate (112 mmol) and 15 g of 1, 4-butanediol (166 mmol) are added, argon is introduced, the mixture is gradually heated to 180 ℃, and the reaction is carried out under the stirring of 100r.p.m, the generated methanol is removed by condensation, and the reaction is stopped when no methanol is generated.
(3) After this time, the temperature was reduced and 0.35 g of magnesium butanediol was added as transesterification catalyst. And gradually heating to 230 ℃, simultaneously connecting an oil pump for vacuum pumping, and carrying out polycondensation reaction for 12 hours under the stirring of the pressure of 30Pa and 100r.p.m to obtain a polyester product.
The polyester product prepared in this example was a non-optically active, fully biodegradable polybutylene succinate having an intrinsic viscosity of 0.91dL/g (chloroform as solvent) and a viscosity average molecular weight of 52kDa, as measured by the viscometry.
The polybutylene succinate prepared in this example has a tensile modulus of 200MPa and a tensile strength of 32MPa, as tested by the tensile test of GB/T1040-1992.
The thermal decomposition temperature of the poly (butylene succinate) is 280 ℃ by DSC thermal analysis test of GB/T19466.1-2004.
Comparative example 1
(1) A250 mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet, a condenser and the like was charged with 15 g of analytically pure 1, 4-butanediol, 16.3 g of dimethyl succinate and 0.35 g of magnesium powder, and then argon gas was introduced thereto, and the temperature was gradually increased to 180 ℃ and stirred at 100 r.p.m. for 12 hours.
(2) Gradually heating to 230 ℃, simultaneously connecting with an oil pump for vacuum pumping, carrying out polycondensation reaction for 12 hours under the stirring of the pressure of 40Pa and 100 r.p.m.
The polyester product prepared in this comparative example was a polybutylene succinate with an intrinsic viscosity of 0.13dL/g (chloroform as solvent) and a molecular weight of 2.7kDa, as measured by the viscosity method.
Comparative example 2
(1) The catalyst was prepared according to the procedure in CN 105461911: 1, 4-butanediol is added into a single-chamber electrolytic cell, a supporting electrolyte is magnesium chloride, a metal magnesium block is taken as an anode, and graphite is taken as a cathode; electrifying direct current, starting voltage of 10V, cathode current density of 200mA, electrolyzing for 12 hours at 60 ℃, and taking out an electrode after electrolysis to obtain white suspension; filtering under reduced pressure, washing the white solid with 1, 4-butanediol, and drying to obtain 0.35 g of white solid;
(2) 16.3 g of dimethyl succinate (112 mmol) and 15 g of 1, 4-butanediol (166 mmol) were charged into a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser and the like, argon gas was introduced, the mixture was gradually heated to 180 ℃ and reacted with stirring at 100 r.p.m., the produced methanol was removed by condensation, and the reaction was stopped until no methanol was produced.
(3) After this time, the temperature was reduced and 0.35 g of magnesium butanediol was added as transesterification catalyst. Gradually heating to 230 ℃, simultaneously connecting an oil pump for vacuum pumping, carrying out polycondensation reaction for 12 hours under the stirring of the pressure of 40Pa and 100r.p.m, and obtaining a polyester product.
According to the viscosity method test, the polyester product prepared by the comparative example has the intrinsic viscosity of 0.20 dL/g (chloroform is used as a solvent), and the molecular weight of the low molecular weight polybutylene succinate is 5 kDa.
Examples 2 to 5
The synthesis process is the same as that of example 1, except that dimethyl succinate in the polyester synthesis process is replaced by dimethyl glutarate, dimethyl adipate, dimethyl pimelate and dimethyl suberate respectively. The viscosity average molecular weight of the obtained polyester product is 47kDa, 40kDa, 29kDa and 22 kDa respectively.
Examples 6 to 9
The synthesis process is the same as that of example 1, except that butanediol in the polyester synthesis process is replaced by pentanediol, hexanediol, heptanediol, and octanediol, respectively. The ester exchange catalyst is replaced by corresponding dihydric alcohol magnesium, and the viscosity average molecular weight of the obtained polyester product is 35kDa, 32kDa, 30kDa and 23 kDa respectively.
Examples 10 to 13
The synthesis process was the same as in example 1 except that the amount of the transesterification catalyst used in the synthesis of the polyester was replaced with 0.05 wt%, 1 wt% and 2 wt%, respectively, based on the total weight of the raw materials. The viscosity average molecular weight of the obtained polyester product is 37kDa, 40kDa and 35kDa respectively.
Example 14
(1) A250 mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet tube, a condenser and the like was charged with 10 g of analytically pure 1, 4-butanediol, 0.35 g of calcium was added, argon was introduced, the mixture was heated to 140 ℃ and reacted for 4 hours under stirring at 100 r.p.m., and 1.8 g of calcium butanediol having a catalytic activity was obtained after cooling, stirring and aging for 1 hour.
(2) Another 250mL three-neck flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet tube, a condenser and the like is taken, 16.3 g of dimethyl succinate (112 mmol) and 15 g of 1, 4-butanediol (166 mmol) are added, argon is introduced, the mixture is gradually heated to 180 ℃, and the reaction is carried out under the stirring of 100r.p.m, the generated methanol is removed by condensation, and the reaction is stopped when no methanol is generated.
(3) After this time, the temperature was reduced and 0.35 g of calcium butanediol was added as transesterification catalyst. Then gradually heating to 230 ℃, simultaneously connecting with an oil pump for vacuum pumping, carrying out polycondensation reaction for 12 hours under the stirring of the pressure of 25Pa and 100r.p.m, and obtaining the non-optical activity fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.72dL/g (chloroform as a solvent) and the molecular weight of 35 kDa.
Example 15
(1) A250 mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet, a condenser and the like was charged with 10 g of an analytically pure 1, 4-butanediol starting material, 0.35 g of strontium was added, argon gas was introduced, the mixture was heated to 100 ℃ and reacted for 5 hours under stirring at 100 r.p.m., and the temperature was lowered, stirred and aged for 1 hour to obtain 1 g of strontium butanediol having a catalytic activity.
(2) Another 250mL three-neck flask equipped with a mechanical stirrer, a thermometer, a nitrogen inlet tube, a condenser and the like is taken, 16.3 g of dimethyl succinate (112 mmol) and 12.3 g of 1, 4-butanediol (137 mmol) are added, argon is introduced, the mixture is gradually heated to 180 ℃, the reaction is carried out under stirring at 100r.p.m, the generated methanol is removed by condensation, and the reaction is stopped when no methanol is generated.
(3) Then, the temperature was reduced, and 0.35 g of strontium butanediol was added as a transesterification catalyst. Heating to 230 ℃, simultaneously connecting with an oil pump for vacuum pumping, carrying out polycondensation reaction for 12 hours under the stirring of the pressure of 32Pa and 100r.p.m, and obtaining the non-optically active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.68dL/g (chloroform as a solvent) and the molecular weight of 31 kDa.
Example 16
(1) The preparation process of magnesium succinate is the same as that of the step (1) in the example 1.
(2) To a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser and the like, 15 g of succinic acid (127 mmol) and 15 g of 1, 4-butanediol (166 mmol) were added, argon gas was introduced, the mixture was gradually heated to 150 ℃ and reacted under stirring at 100 r.p.m., generated water was removed by a water separator, and the reaction was stopped when sufficient reaction was completed until no water was generated.
(3) And (2) gradually heating the reactants to 230 ℃, simultaneously vacuumizing by connecting an oil pump, and carrying out polycondensation reaction for 12 hours under the stirring of the pressure of 23Pa and 100r.p.m to obtain the non-optically-active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 0.86dL/g (chloroform as a solvent) and the molecular weight of 48 kDa.
Examples 17 to 20
The synthesis process is the same as that of example 16, except that succinic acid in the polyester synthesis process is replaced by glutaric acid, adipic acid, pimelic acid, suberic acid. The viscosity average molecular weight of the obtained polyester product is 58kDa, 43kDa, 36kDa and 31kDa respectively.
Example 21
(1) The procedure for preparing calcium butanediol was the same as in step (1) of example 14.
(2) To a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer, a nitrogen introduction tube, a condenser and the like, 15 g of succinic acid (127 mmol) and 15 g of butanediol (166 mmol) were added, argon gas was introduced, the mixture was gradually heated to 160 ℃ and reacted with stirring at 100 r.p.m., and the generated water was removed by a water separator and the reaction was stopped when no water was generated.
(3) Adding 0.35 g of calcium butanediol into the reaction system, gradually heating to 230 ℃, simultaneously vacuumizing by a connecting oil pump under the pressure of 22Pa, and carrying out polycondensation reaction for 12 hours under the stirring of 100r.p.m to obtain the non-optically-active fully biodegradable poly (butylene succinate) with the intrinsic viscosity of 1.04dL/g (chloroform as a solvent) and the molecular weight of 62 kDa.
Claims (6)
1. A method for synthesizing biodegradable polyester with bioactivity is characterized by specifically comprising the following steps:
prepolymerization reaction: carrying out prepolymerization reaction on any one of dicarboxylic acid and dibasic ester and excessive dihydric alcohol B to prepare a prepolymer; the temperature of the prepolymerization reaction is 80-230 ℃;
ester exchange reaction: performing transesterification reaction on the prepolymer in the presence of a transesterification catalyst to obtain the biodegradable polyester with bioactivity; the temperature of the ester exchange reaction is 120-260 ℃, and the time is 6-24 hours;
the synthesis method of the transesterification catalyst comprises the following steps:
mixing the simple substance M with the dihydric alcohol A, heating to a temperature above the boiling point of the dihydric alcohol A, reacting under the condition of condensation and reflux, and stirring and aging to obtain the ester exchange catalyst;
the elementary substance M is at least one selected from metal magnesium, calcium and strontium;
the structural general formula of the dihydric alcohol A is HO (CH)2)mOH, m is selected from 2-10;
the mass ratio of the simple substance M to the dihydric alcohol A is 0.001-0.5: 1;
the dihydric alcohol A is the dihydric alcohol B.
2. The method for synthesizing biodegradable polyester with bioactivity according to claim 1, wherein in the prepolymerization reaction:
the structural general formula of the dicarboxylic acid is HOOC (CH)2)xCOOH, x is selected from 0 or 2-8;
the structural general formula of the dibasic ester is CH3(CH2)yOOC(CH2)zCOO(CH2)yCH3Y is selected from 0 or 1, and z is selected from 0-8;
the structural general formula of the dihydric alcohol B is HO (CH)2)nOH and n are selected from 2-10;
the molar ratio of any one of dicarboxylic acid and diester to diol is 1: 1.1 to 5.
3. The method for synthesizing biodegradable polyester with bioactivity according to claim 1, wherein the prepolymerization reaction is carried out under the protection of inert atmosphere until no small molecule by-product is produced, and then the next transesterification reaction is carried out.
4. The method for synthesizing biodegradable polyester according to claim 1, wherein the amount of the transesterification catalyst is 0.001-10 wt% based on the total mass of the raw materials.
5. The method for synthesizing biodegradable polyester according to claim 1, wherein the transesterification is performed under reduced pressure and vacuum degree is 0.1-80 Pa.
6. A biodegradable polyester having biological activity synthesized according to the method of any one of claims 1 to 5.
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